EP2690155A1 - Promoteur d'orientation de cristaux liquides, composition de cristaux liquides, matériau polymère et film - Google Patents

Promoteur d'orientation de cristaux liquides, composition de cristaux liquides, matériau polymère et film Download PDF

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EP2690155A1
EP2690155A1 EP12760462.7A EP12760462A EP2690155A1 EP 2690155 A1 EP2690155 A1 EP 2690155A1 EP 12760462 A EP12760462 A EP 12760462A EP 2690155 A1 EP2690155 A1 EP 2690155A1
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Prior art keywords
group
carbon atoms
liquid crystalline
liquid crystal
formula
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EP12760462.7A
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German (de)
English (en)
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EP2690155A4 (fr
EP2690155B1 (fr
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Masatoshi Mizumura
Shunya Katoh
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Fujifilm Corp
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Fujifilm Corp
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    • C09K2019/181—Ph-C≡C-Ph
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    • C09K2019/2035—Ph-COO-Ph
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Definitions

  • the present invention relates to a liquid crystal orientation promoter useful in a variety of uses including materials of a variety of optical members, such as an optical anisotropic film and a heat shielding film, a liquid crystalline composition including the promoter, a macromolecular material, and a film for which the liquid crystalline composition and the macromolecular material are used.
  • a liquid crystal orientation promoter useful in a variety of uses including materials of a variety of optical members, such as an optical anisotropic film and a heat shielding film, a liquid crystalline composition including the promoter, a macromolecular material, and a film for which the liquid crystalline composition and the macromolecular material are used.
  • liquid crystals When coated on a film on which an orientation treatment has been carried out (oriented film), liquid crystals are regularly oriented. In addition, the orientation state of liquid crystals can be controlled by sandwiching the liquid crystals between two oriented films. Therefore, in a liquid crystal display apparatus made up of a liquid crystal cell made up of rod-shaped liquid crystalline molecules and two substrates for sealing the molecules and an electrode layer for applying a voltage to the rod-shaped liquid crystalline molecules, since a state in which the rod-shaped liquid crystalline molecules are injected into gaps in the oriented film formed on the two substrates is formed, it is possible to relatively easily control the orientation state of the rod-shaped liquid crystalline molecules.
  • an optical compensation sheet (wave plate) is disposed between the liquid crystal cell and a polarization plate.
  • an optical anisotropic element having an optical anisotropic layer formed of liquid crystalline molecules on a transparent support is used as the optical compensation sheet.
  • the optical anisotropic layer is formed by orienting the liquid crystalline molecules and fixing the orientation state.
  • the liquid crystalline molecules are oriented using one oriented film provided between the transparent support and the optical anisotropic layer.
  • Patent Literature 1 attempts are being made to develop techniques that uniformly orient liquid crystals on the side of the interface on which an orientation treatment has not been carried out (the air interface) by supplying an orientation restraining force even when no oriented film is provided.
  • the orientation of the liquid crystalline molecules is controlled by adding a liquid crystal orientation promoter.
  • a liquid crystalline composition in which liquid crystalline molecules are easily and uniformly oriented using a liquid crystal orientation promoter is provided.
  • an object of the invention is to solve the problems of the related art and to provide a material that exhibits a sufficient solubility, has a wide available concentration range, and exhibits excellent liquid crystal orientation promoting properties.
  • another obj ect is to provide a new liquid crystalline composition in which liquid crystalline molecules are easily and uniformly oriented using the above material.
  • the object of the invention is to provide a liquid crystal orientation promoter useful in a variety of uses including materials of a variety of optical members, such as an optical anisotropic film and a heat shielding film, a liquid crystalline composition including the promoter, a macromolecular material, and a film for which the liquid crystalline composition and the macromolecular material are used.
  • a liquid crystal orientation promoter useful in a variety of uses including materials of a variety of optical members, such as an optical anisotropic film and a heat shielding film, a liquid crystalline composition including the promoter, a macromolecular material, and a film for which the liquid crystalline composition and the macromolecular material are used.
  • Means for achieving the above object is as follows.
  • a liquid crystalline composition useful in a variety of uses including materials of a variety of optical members, such as an optical anisotropic film and a heat shielding film, a macromolecular material, and a film for which the liquid crystalline composition and the macromolecular material are used by using an orientation promoter represented by the formula (I) which has a wide available concentration range, a high solvent solubility and a favorable liquid crystal orientation promoting action.
  • an orientation promoter represented by the formula (I) which has a wide available concentration range, a high solvent solubility and a favorable liquid crystal orientation promoting action.
  • numeric ranges expressed using "to” in the present specification include numeric values before and after "to" as the lower limit value and the upper limit value.
  • the liquid crystal orientation promoter of the invention contains a compound represented by the following formula (I).
  • the compound of the following formula (I) has a divalent group in the center, and has an alkyl fluoride group at the end.
  • a compound having an alkyl fluoride group at the end is effective as an orientation promoter, but known orientation promoters of the related art had narrow available concentration ranges and low solubility, and thus were used in limited ranges.
  • the compound of the following formula (I) exhibits equal or better orientation performances in a wider concentration range with a more favorable solubility, and therefore a composition including the above compound has a merit of being easily used for manufacturing the composition.
  • the composition can be cured through polymerization, the composition is useful in a variety of uses, such as optical members.
  • each of L 1 , L 2 , L 3 , L 4 , L 5 and L 6 independently represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -COS-, -SCO-, -NRCO- or -CONR- (R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), more preferably represents -O-, -S-, -CO-, -COO-, -OCO-, -COS- or -SCO-, and still more preferably represents -O-, -CO-, -COO-or -OCO-.
  • the alkyl group that can be used as the R may have a linear shape or a branched shape, more preferably has 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group and an n-propyl group.
  • Sp represents a single bond or an alkylene group having 1 to 10 carbon atoms, more preferably represents a single bond or an alkylene group having 1 to 7 carbon atoms, and still more preferably a single bond or an alkylene group having 1 to 4 carbon atoms.
  • Non-adjacent methylene groups in the alkylene may be substituted by -O-, -S-, -CO-, -COO-, -OCO-, -COS-, -SCO-, -NRCO-, -CONR- or -OH.
  • the alkylene group may or may not have branches, but is preferably a linear alkylene group having no branch.
  • a 1 and A 2 represent divalent aromatic hydrocarbon groups or divalent heterocyclic groups, and more preferably divalent aromatic hydrocarbons.
  • the divalent aromatic hydrocarbon group has a number of carbon atoms of preferably 6 to 22, more preferably 6 to 14, still more preferably 6 to 10, and is most preferably a phenylene group.
  • the phenylene groups preferably have atomic bonds at meta positions or para positions, and particularly preferably have atomic bonds at para positions.
  • the divalent heterocyclic group preferably has a 5-membered, 6-membered or 7-membered heterocyclic ring.
  • a 5-membered ring or 6-membered ring is more preferable, and a 6-membered ring is most preferable.
  • a heteroatom that configures the heterocyclic ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
  • the heterocyclic ring is preferably an aromatic heterocyclic ring.
  • the aromatic heterocyclic ring is generally an unsaturated heterocyclic ring. An unsaturated heterocyclic ring having most double bonds is more preferable.
  • heterocyclic ring examples include a furan ring, a thiophene ring, a pyrrole ring, a pyrroline ring, a pyrrolidine ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an imidazoline ring, an imidazolidine ring, a pyrazole ring, a pyrazoline ring, a pyrazolidine ring, a triazole ring, a furazan ring, a tetrazole ring, a pyran ring, a thiine ring, a pyridine ring, a piperidine ring, an oxazine ring, a morpholine ring, a thiazine ring, a pyridazine ring, a pyrimizine ring, a a
  • the divalent aromatic hydrocarbon group or the divalent heterocyclic ring group represented by A 1 and A 2 may have a substituent.
  • the substituent include an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a cyano group and an ester group.
  • the following corresponding description of T can be referenced.
  • the substituent with respect to the divalent aromatic hydrocarbon group or the divalent heterocyclic ring group represented by A 1 and A 2 include a methyl group, an ethyl group, a methoxy group, an ethoxy group, a bromine atom, a chlorine atom, a cyano group and the like.
  • a 1 and A 2 are preferably equal.
  • T represents a divalent group or a divalent aromatic heterocyclic group represented by (X represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogen atom, a cyano group or -COOR 0 (R 0 represents a hydrogen atom, an alkyl group or an alkyl fluoride group in which an adjacent CH 2 may be substituted by O or S, or -Sp 5 -P, Sp 5 represents a single bond or an alkylene group having 1 to 10 carbon atoms (here, a hydrogen atom in the alkylene group may be substituted by a fluorine atom), and P represents a polymerizable group), and each of Ya, Yb, Yc and Yd independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), is more preferably , and still more preferably
  • the number of carbon atoms in the alkyl group that can be used as X is 1 to 8, preferably 1 to 5, and
  • the alkyl group may have any of a linear shape, a branched shape and a cyclic shape, and preferably has a linear shape or a branched shape.
  • Examples of the preferable alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like.
  • alkyl portion of the alkoxy group that can be used as X the description and preferable range of the alkyl group that can be used as X can be referenced.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom and a bromine atom are preferable.
  • Examples of the ester group that can be used as X include groups represented by RCOO-.
  • Examples of R include an alkyl group having 1 to 8 carbon atoms. Regarding the description and preferable range of the alkyl group that can be used as R, the description and preferable range of the alkyl group that can be used as X can be referenced. Specific examples of the ester include CH 3 COO- and C 2 H 5 COO-. In -COOR 0 , R 0 represents a hydrogen atom, an alkyl group or an alkyl fluoride group in which an adjacent CH 2 may be substituted by O or S, or -Sp 5 -P.
  • R 0 represents an alkyl group or an alkyl fluoride group in which an adjacent CH 2 may be substituted by O or S
  • R 0 is more preferably a group represented by -Sp 6 -(L 7 -Sp 7 ) q -CH 3 or a group represented by -Sp 8 -(L 8 -Sp 9 ) r -Hb 0 .
  • Each of Sp 6 , Sp 7 , Sp 8 and Sp 9 independently represents a single bond or an alkylene group having 1 to 10 carbon atoms, is preferably a single bond or an alkylene group having 1 to 7 carbon atoms, and more preferably a single bond or an alkylene group having 1 to 4 carbon atoms.
  • a hydrogen atom in the alkylene group represented by Sp 6 , Sp 7 , Sp 8 and Sp 9 may be substituted by a fluorine atom, but is preferably not substituted, and the alkylene group may or may not have a branch, but is preferably a linear alkylene group having no branch.
  • Each of L 7 and L 8 independently represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -COS-, -SCO-, -NRCO- or -CONR-(R in L 7 and L 8 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).
  • L 7 and L 8 are preferably -O-, -S-, -CO-, -COO-, -OCO-, -COS- or -SCO-, more preferably -O-, -CO-, -COO- or -OCO- from the viewpoint of the stability of the compound, and still more preferably -O-.
  • q represents an integer of 1 to 4, is preferably an integer of 1 to 3, more preferably 2 or 3, and particularly preferably 3.
  • r represents an integer of 1 to 4, is preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1.
  • each of a plurality of L 7 , L 8 , Sp 7 and Sp 9 may be independent or different.
  • Hb 0 represents a perfluoroalkyl group or a fluoroalkyl group having 2 to 30 carbon atoms, is more preferably a perfluoroalkyl group or a fluoroalkyl group having 3 to 20 carbon atoms, and still more preferably a perfluoroalkyl group or a fluoroalkyl group having 3 to 10 carbon atoms.
  • the perfluoroalkyl group or the fluoroalkyl group may have any of a linear shape, a branched shape and a cyclic shape, but preferably has a linear shape or a branched shape, and more preferably has a linear shape.
  • the Hb 0 is preferably the perfluoroalkyl group having 2 to 30 carbon atoms.
  • Sp 5 represents a single bond or an alkylene group having 1 to 10 carbon atoms, is preferably a single bond or an alkylene group having 1 to 7 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms.
  • a hydrogen atom in the alkylene group represented by Sp 5 may be substituted by a fluorine atom, and the alkylene group may or may not have a branch, but is preferably a linear alkylene group having no branch.
  • the P represents a polymerizable group
  • the polymerizable group is not particularly limited, but preferably an ethylenic unsaturated double-bonded group, more preferably a methacryloyl group or an acryloyl group, and particularly preferably an acryloyl group.
  • the alkyl group having 1 to 4 carbon atoms that can be used as Ya, Yb, Yc and Yd may have a linear shape or a branched shape. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like.
  • the description and explanation of the aromatic heterocyclic group of the following A 1 and A 2 can be referenced.
  • Hb represents an alkyl fluoride group having 3 to 30 carbon atoms, is more preferably an alkyl fluoride group having 3 to 20 carbon atoms, and still more preferably an alkyl fluoride group having 3 to 10 carbon atoms.
  • the alkyl fluoride group may or may not be substituted by hydrogen.
  • the alkyl fluoride group may have any of a linear shape, a branched shape and a cyclic shape, but preferably has a linear shape or a branched shape, and more preferably has a linear shape.
  • Preferable examples of the alkyl fluoride group include an alkyl fluoride group having a perfluoroalkyl group at the end. That is, the alkyl fluoride group is preferably a group represented by the following formula. (C p F 2p+1 ) - (C q H 2q ) -
  • p is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10.
  • q is preferably 0 to 20, more preferably 0 to 10, and still more preferably 0 to 5.
  • p+q is 3 to 30.
  • k, l, m, n and p represent integers of 0 or more, and o is any integer of 1 to 4.
  • k, l, m, n, o and p are 2 or more, a plurality of structures in parentheses may be equal or different.
  • k, l, m and n in the formula (I) are preferably any integers of 0 to 6, more preferably any integers of 0 to 4, still more preferably any integers of 0 to 3, and most preferably any integers of 0 to 2.
  • o is preferably 1 or 2.
  • p is preferably any integer of 1 to 4, and more preferably 1 or 2.
  • the compound represented by the formula (I) may have a symmetric molecular structure or may have an asymmetric molecular structure.
  • the symmetric molecular structure mentioned herein refers to any of point-symmetric, line-symmetric and rotation-symmetric molecular structures
  • the asymmetric molecular structure refers to a molecular structure that does not belong to any of point-symmetric, line-symmetric and rotation-symmetric molecular structures.
  • the compound represented by the formula (I) is a compound in which the above-described alkyl fluoride group (Hb), a linking group (L 1 ) k -Sp-(L 2 -A 1 ) l -L 3 and -L 4 - (A 2 -L 5 ) m -Sp-(L 6 ) n and T, which is a divalent group having an excluded volume effect, are combined.
  • Two alkyl fluoride groups (Hb) present in the molecule are preferably mutually equal, and the linking groups present in the molecule (L 1 ) k -Sp-(L 2 -A 1 ) l -L 3 and -L 4 -(A 2 -L 5 ) m -Sp-(L 6 ) n are also preferably mutually equal.
  • Hb-(L 1 ) k -Sp- and -Sp- (L 6 ) n -Hb at the ends are preferably groups represented by any of the following formulae.
  • p is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10.
  • q is preferably 0 to 20, more preferably 0 to 10, and still more preferably 0 to 5.
  • p+q is 3 to 30.
  • r is preferably 1 to 10, and more preferably 1 to 4.
  • Hb-(L 1 ) k -Sp-L 2 - and -L 5 -Sp-(L 6 ) n -Hb at the ends are preferably groups represented by any of the following formulae.
  • the compound represented by the formula (I) can be synthesized by appropriately selecting and combining the synthesizing methods described in JP-A-2002-129162 , JP-A-2002-97170 or documents cited in the above publications.
  • the compound can be synthesized by combining other well-known synthesizing methods as necessary.
  • the liquid crystalline composition of the invention includes polymerizable liquid crystalline molecules and the compound represented by the formula (I).
  • one or more kinds of polymerizable liquid crystalline molecules and one or more kinds of non-polymerizable liquid crystalline molecules may be jointly used.
  • two or more of the compounds represented by the formula (I) may be used, and the compound represented by the formula (I) and another liquid crystal orientation promoter may be jointly used.
  • the liquid crystal orientation promoter is preferably used in an amount of 0.01 mass% to 20 mass% of the amount of the liquid crystalline molecules.
  • the use amount is preferably an amount of 0.1 mass% to 5 mass%.
  • Discotic liquid crystalline molecules or rod-shaped liquid crystalline molecules are preferably used as the polymerizable liquid crystalline molecules.
  • the discotic liquid crystalline molecules are described in a variety of documents ( C. Destrade et at., Mol. Crysr. Liq. Cryst., Vol. 71, page 111 (1981 ); Quarterly Chemical Review by the Chemical Society of Japan No. 22, Chemistry of Liquid Crystals, Chapter 5, Section 2 of Chapter 10 (1994 ); B. Kohne et al., Angew. Chem. Soc. Chem. Comm., page 1794 (1985 ) ; J. Zhang et al., J. Am. Chem. Soc., vol. 116, page 2655 (1994 )).
  • the polymerization of the discotic liquid crystalline molecules is described in JP-A-8-27284 .
  • the discotic liquid crystalline molecule having a polymerizable group is preferably a compound represented by the following formula. D(-L-Q)n
  • D represents the discotic core
  • L represents a divalent linking group
  • Q represents a polymerizable group
  • n represents an integer of 4 to 12.
  • LQ or QL
  • D4 is particularly preferable.
  • the birefringence of the polymerizable rod-shaped liquid crystalline molecules is preferably 0.001 to 0.7.
  • the rod-shaped liquid crystalline molecules preferably have a molecular structure that is almost symmetric with respect to the short-axis direction. In order to have such a molecular structure, the rod-shaped liquid crystalline molecules preferably have polymerizable groups at both ends of the rod-shaped molecular structure.
  • specific examples of the rod-shaped liquid crystalline molecules will be illustrated.
  • the liquid crystalline composition can include a solvent, a compound including an asymmetric carbon atom, a polymerization initiator (described below) or other additives (for example, cellulose esters) as necessary in addition to the polymerizable liquid crystalline molecules and the liquid crystal orientation promoter.
  • An organic solvent is preferably used as the solvent for the liquid crystalline composition.
  • organic solvent examples include amides (for example, N,N-diemthylformamide), sulfoxides (for example, dimethyl sulfoxide), hetero ring compounds (for example, pyridine), hydrocarbons (for example, benzene and hexane), alkyl halides (for example, chloroform and dichloromethane), esters (for example, methyl acetate and butyl acetate) , ketones (for example, acetone and methyl ethyl ketone) and ethers (for example, tetrahydrofuran and 1,2-dimethoxyethane). Alkyl halides and ketones are preferable. Two or more organic solvents may be jointly used.
  • amides for example, N,N-diemthylformamide
  • sulfoxides for example, dimethyl sulfoxide
  • hetero ring compounds for example, pyridine
  • hydrocarbons for example, benzene and hexane
  • a film by manufacturing a film using a method such as coating of a liquid crystalline composition including the compound represented by the formula (I). It is also possible to produce an optically anisotropic element by coating a liquid crystalline composition on an oriented film and forming a liquid crystalline layer.
  • the liquid crystalline composition can be coated using a well-known method (for example, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a die coating method or a bar coating method).
  • the liquid crystalline molecules are preferably fixed while maintaining the orientation state.
  • the liquid crystalline molecules are preferably fixed using a polymerization reaction of the polymerizable group (Q) introduced into the liquid crystalline molecules.
  • the polymerization reaction include a thermopolymerization reaction in which a thermopolymerization initiator is used and a photopolymerization reaction in which a photopolymerization initiator is used.
  • the photopolymerization reaction is preferable.
  • Examples of the photopolymerization initiator include ⁇ -carbonyl compounds (described in the respective specifications of U.S. Patent No. 2367661 and U.S. Patent No. 2367670 ), acyloin ethers (described in the specification of U.S. Patent No. 2448828 ), ⁇ -hydrocarbon-substituted aromatic acyloin compounds (described in the specification of U.S. Patent No. 2722512 ), polynuclear quinone compounds (described in the respective specifications of U.S. Patent No. 3046127 and U.S. Patent No.
  • the use amount of the photopolymerization initiator is preferably 0.01 mass% to 20 mass%, and more preferably 0. 5 mass% to 5 mass% of the solid content of a coating fluid.
  • Ultraviolet rays are preferably used for light radiation for polymerizing the discotic liquid crystalline molecules.
  • the radiation energy is preferably 20 mJ/cm 2 to 50 J/cm 2 , and more preferably 100 mJ/cm 2 to 800 mJ/cm 2 .
  • light radiation may be carried out under heating conditions.
  • the thickness of the liquid crystalline layer is preferably 0.1 ⁇ m to 50 ⁇ m, more preferably 1 ⁇ m to 30 ⁇ m, and most preferably 5 ⁇ m to 20 ⁇ m.
  • the coating amount of the liquid crystal orientation promoter in the liquid crystalline layer is preferably 0.005 g/m 2 to 0.5 g/m 2 , more preferably 0.01 g/m 2 to 0.45 g/m 2 , still more preferably 0.02 g/m 2 to 0.4 g/m 2 , and most preferably 0.03 g/m 2 to 0.35 g/m 2 .
  • the oriented film can be provided using means such as a rubbing treatment of an organic compound (preferably a polymer), oblique deposition of an inorganic compound, formation of a layer having microgrooves or accumulation of an organic compound (for example, ⁇ -tricosanoic acid, dioctadecyl methyl ammonium chloride or methyl stearate) using a Langmuir Blodgett method (LB film).
  • LB film Langmuir Blodgett method
  • oriented films in which an orientation function is generated by supply of an electric field, supply of a magnetic field or radiation of light are also known.
  • An oriented film formed using a rubbing treatment of a polymer is particularly preferable.
  • the rubbing treatment is carried out by rubbing the surface of a polymer layer with paper or fabric in a certain direction several times.
  • the kind of the polymer used in the oriented film is determined depending on the orientation of the liquid crystalline molecules (particularly an average inclination angle).
  • a polymer that does not decrease the surface energy of the oriented film is used in order to orient the liquid crystalline molecules horizontally (average inclination angle: 0° to 50°).
  • a polymer that decreases the surface energy of the oriented film is used in order to orient the liquid crystalline molecules vertically (average inclination angle: 50° to 90°).
  • a polymer that decreases the surface energy of the oriented film is used.
  • the kinds of specific polymers are described in documents regarding optical compensation sheets in which liquid crystalline molecules corresponding to a variety of display modes are used.
  • the thickness of the oriented film is preferably 0.01 ⁇ m to 5 ⁇ m, and more preferably 0.05 ⁇ m to 1 ⁇ m.
  • the liquid crystalline layer may be transferred onto a transparent support after orienting the liquid crystalline molecules in an optically anisotropic layer using the oriented film.
  • the liquid crystalline molecules fixed in an oriented state can maintain the oriented state without the oriented film.
  • an orientation having an average inclination angle of less than 5° it is not necessary to carry out the rubbing treatment, and the oriented film is not required either.
  • an oriented film that forms a chemical bond with the liquid crystalline molecules at an interface may be used for the purpose of improving adhesion between the liquid crystalline molecules and the transparent support.
  • the rubbing treatment may not be carried out.
  • the liquid crystalline layer formed on the transparent support it is also possible to make the liquid crystalline layer formed on the transparent support function as the oriented film for the liquid crystalline layer provided thereon.
  • the film of the invention or an optically anisotropic element having the film of the invention may have a transparent support.
  • a transparent support a glass plate or a polymer film is used, and a polymer film is preferably used.
  • the support being transparent means that the light transmittance is 80% or more.
  • an optically isotropic polymer film is used as the transparent support.
  • the polymer film being optically isotropic means that, specifically, the in-plane retardation (Re) is preferably less than 10 nm, and more preferably less than 5 nm.
  • the retardation (Rth) in a thickness direction is also preferably less than 10 nm, and more preferably less than 5 nm.
  • Re nx - ny d
  • Rth nx + ny / 2 - nz d
  • nx and ny represent the in-plane refractive indexes of the transparent support
  • nz represents the refractive index of the transparent support in the thickness direction
  • d represents the thickness of the transparent support.
  • the transparent support is preferably optically uniaxial or biaxial.
  • the support may be optically positive (the refractive index in the light axis direction is larger than the refractive index in the direction perpendicular to the light axis) or negative (the refractive index in the light axis direction is smaller than the refractive index in the direction perpendicular to the light axis).
  • the refractive indexes nx, ny and nz in the above-described formulae all become different values (nx ⁇ ny ⁇ nz).
  • the in-plane retardation (Re) of the optically anisotropic transparent support is preferably 10 nm to 1000 nm, more preferably 15 nm to 300 nm, and most preferably 20 nm to 200 nm.
  • the retardation (Rth) in the thickness direction of the optically anisotropic transparent support is preferably 10 nm to 1000 nm, more preferably 15 nm to 300 nm, and still more preferably 20 nm to 200 nm.
  • a material that forms the transparent support is determined depending on whether the support is optically isotropic or optically anisotropic.
  • the optically isotropic support in general, glass or cellulose esters are used.
  • the optically anisotropic support in general, a synthetic polymer (for example, a polycarbonate, a polysulfone, a polyethersulfone, a polyacrylate, a polymethacrylate or a norbornene resin) is used.
  • an optically anisotropic cellulose ester film (having a high retardation) through (1) use of a retardation enhancer, (2) a decrease in the acetylation degree of cellulose acetate or (3) manufacturing of a film using a cooling solution method which is described in the specification of European Patent No. 0911656A2 .
  • a transparent support made of a polymer film is preferably formed using a solvent casting method.
  • a stretching treatment is preferably carried out on a polymer film.
  • an ordinary uniaxial stretching treatment or an ordinary biaxial stretching treatment may be carried out.
  • an unbalanced biaxial stretching treatment is preferably carried out.
  • unbalanced biaxial stretching a polymer film is stretched in a certain direction at a certain scaling factor (for example, 3% to 100%, and preferably 5% to 30%), and stretched in a direction perpendicular to the former direction at an equal or larger scaling factor (for example, 6% to 200%, and preferably 10% to 90%).
  • the stretching treatments in the two directions may be carried out at the same time.
  • the stretching direction (in the unbalanced biaxial stretching, the direction with a larger stretching scaling factor) and the in-plane slow axis of the stretched film preferably become substantially the same direction.
  • the angle between the stretching direction and the slow axis is preferably less than 10°, more preferably less than 5°, and most preferably less than 3°.
  • the thickness of the transparent support is preferably 10 ⁇ m to 500 ⁇ m, and more preferably 50 ⁇ m to 200 ⁇ m.
  • a surface treatment for example, a glow discharge treatment, a corona discharge treatment, an ultraviolet (UV) treatment or a flame treatment
  • An ultraviolet absorbent may be added to the transparent support.
  • An adhesion layer (basecoat layer) may be provided on the transparent support.
  • the adhesion layer is described in JP-A-7-333433 .
  • the thickness of the adhesion layer is preferably 0.1 ⁇ m to 2 ⁇ m, and more preferably 0.2 ⁇ m to 1 ⁇ m.
  • a compound (1) was synthesized using the following route.
  • the ester (1b) (26.5 g, 55 mmol) and parahydroxybenzaldehyde (6.1 g, 50 mmol) were reacted in DMAc (30 ml) in the presence of potassium carbonate (7.6 g, 55 mmol) at 90°C over 2 hours.
  • an aldehyde (1c) was obtained using a condensation operation as a crude substance. The aldehyde was used as it was in the subsequent steps without being purified.
  • a carboxylic acid (1d) was derived from the aldehyde (1c) using the method described in [0085] to [0087] on page 10 of JP-A-2002-97170 (15.2 g, total percentage yield from ester (1b) 65%)
  • a compound (2) was synthesized using the following route.
  • the tosyl derivative (2b) (16.2 g, 50 mmol) and an alcohol fluoride (2c) (12.1 ml, 55 ml) were added to toluene (100 ml), and an aqueous solution of benzyltrimethlyammonium hydroxide (105 ml) was added.
  • the solution was heated to 70°C, stirred for 30 minutes, and then an aqueous solution of potassium hydroxide (3.1 g/ 20 ml of water) was added. After that, the solution was heated to 80°C, and reacted over 5 hours.
  • the ether (2d) (20. 0 g, 40 mmol) was reacted with hydrogen in ethyl acetate (40 ml) in the presence of a palladium catalyst (1.2 g, 5% palladium/active carbon, Degussa-type E101 O/W 5% Pd, manufactured by Wako Pure Chemical Industries, Ltd.). After the completion of the reaction, the palladium catalyst was removed through celite filtration, and the solution was condensed, thereby obtaining a crude substance of an alcohol (2e). The alcohol was used as it was as a raw material in the subsequent steps without being purified.
  • a palladium catalyst 1.2 g, 5% palladium/active carbon, Degussa-type E101 O/W 5% Pd, manufactured by Wako Pure Chemical Industries, Ltd.
  • the alcohol (2e) (18.0 g, 45 mmol) was added to ethyl acetate (30 ml), and cooled using ice. The temperature of a reaction system was maintained at 20°C or lower, and methanesulfonyl chloride (3.8 ml, 49.5 mmol) was added dropwise. The solution was reacted at room temperature over 3 hours, liquids were separated using ethyl acetate and water, and the solution was condensed, thereby obtaining a crude substance of methanesulfonate ester (2f). The methanesulfonate ester was used as it was as a raw material in the subsequent steps without being purified.
  • the ester (2f) (18.5 g, 42.8 mmol) and parahydroxybenzaldehyde (5.22 g, 42.8 mmol) were reacted in DMAc (40 ml) in the presence of potassium carbonate (6.51 g, 47.1 mmol) at 90°C, thereby obtaining a crude substance of an aldehyde (2 g).
  • the aldehyde (2g) (10.5 g) was obtained through column purification.
  • a carboxylic acid (2h) was derived from the aldehyde (2 g) (10.5 g, 20.5 mmol) using the method described in [0085] to [0087] on page 10 of JP-A-2002-97170 (8.2 g, percentage yield 76%)
  • a compound (64) was synthesized using the following route.
  • Synthesis can be performed up to a carboxylic acid (3a) via a route described below using a well-known synthesis method.
  • the carboxylic acid (3a) (2.34 g, 4.0 mmol) was reacted with toluene (10 ml) and a catalytic amount of thionyl chloride (0.44 ml, 6.0 mmol) in DMF so as to produce an acid chloride, excess thionyl chloride and excess toluene were removed, and then THF (5 ml) was added to the system.
  • Methylhydroquinone 124 mg, 2.0 mmol
  • THF 5 ml
  • diisopropylethylamine (0.77 ml) was added dropwise. After a liquid separation operation, the solution was condensed using an evaporator, and recrystallized using ethyl acetate/methanol, thereby obtaining a compound (64) (0.79 g, 31%).
  • a compound (4) was obtained using the same operations as in Synthesis Example 2 except that 4-amino-m-cresol was used instead of methylhydroquinone in Synthesis Example 2.
  • a compound (73) was synthesized using the following route.
  • a compound (73) was synthesized in the same manner except that the compound (5a) was used instead of methylhydroquinone in the synthesis of the compound (2).
  • Optically anisotropic films were formed using liquid crystal orientation promoters described in Table 1, and evaluated.
  • coating fluids having the following compositions were prepared.
  • the liquid crystal orientation promoters were prepared so that the concentrations became 0.01 parts by mass, 0.10 parts by mass and 0.20 parts by mass with respect to a rod-shaped liquid crystalline compound.
  • Rod-shaped liquid crystalline compound 1 described below 100 parts by mass Chiral agent (A) described below 2.8 parts by mass IRGACURE 819 (manufactured by Ciba Japan K.K.) 3 parts by mass Liquid crystal orientation promoter described 1 in Table above amount
  • the prepared coating fluid was taken in an amount of 50 ⁇ l using a micropipette, added dropwise to an oriented film-attached glass plate (SE-130), and spin-coated at a rotation rate of 2000 rpm.
  • the coating fluid was heated at 85°C for 2 minutes, cooled in the air for 1 minute, and then irradiated with ultraviolet rays in a nitrogen atmosphere (ultraviolet ray intensity: 500 mJ/m 2 ), thereby forming an optically anisotropic film.
  • the film thickness of the optically anisotropic film was approximately 5 ⁇ m.
  • the orientation properties of the respective prepared optically anisotropic films were evaluated through visual checking and haze.
  • the haze was measured using a haze meter NDH 2000 manufactured by Nippon Denshoku Co., Ltd.
  • the orientation promotion actions of the liquid crystal orientation promoters were evaluated by the following 4 levels based on the haze values of the optically anisotropic films in which the concentrations of the liquid crystal orientation promoters were 0.01 mass%. It is indicated that, at a concentration of 0.01 mass%, the liquid crystal orientation promoter is fully dissolved in a solvent, and the liquid crystal orientation promotion action is enhanced as the measured haze value decreases.
  • the dissolution and orientation promotion actions were evaluated by the following 4 levels based on the haze values of the optically anisotropic films in which the concentrations of the liquid crystal orientation promoters were 0.10 mass% and 0.20 mass%.
  • Favorable evaluation indicates that the solubility is favorable and the orientation promotion action is also large.
  • Poor evaluation indicates that, mainly, the solubility is poor.
  • the liquid crystal orientation promoter of the invention has a large liquid crystal orientation action and a high solubility in a solvent even at a high concentration.
  • the promoter exhibits the same tendency even in different solvents, and the liquid crystal orientation promoter of the invention has a wide application range of a coating solvent and a high usage aptitude.

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EP12760462.7A 2011-03-24 2012-03-22 Promoteur d'orientation de cristaux liquides, composition de cristaux liquides, matériau macromoléculaire et film Active EP2690155B1 (fr)

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WO2012128306A1 (fr) 2012-09-27
US9290697B2 (en) 2016-03-22
EP2690155A4 (fr) 2014-10-29
CN103443246A (zh) 2013-12-11
EP2690155B1 (fr) 2017-10-25
US20140014877A1 (en) 2014-01-16
JP5750069B2 (ja) 2015-07-15
JP2012211306A (ja) 2012-11-01

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